CN103554176A - Thiophosphoryl compounds - Google Patents
Thiophosphoryl compounds Download PDFInfo
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Abstract
The invention provides a group of thiophosphoryl compounds. The compounds have a general formula shown in the specification, wherein X is S or O; R1 is ethyl or 2-chloro-4-bromophenyl; R is any one of S-3-methyl-2-(4-chlorphenyl)butyryl, 4-methoxyene-2-(p-chlorphenyl)-3-cyano-5-(trifluoromethyl)pyrryl, 4-methylmercapto-2-(p-chlorphenyl)-3-cyano-5-(trifluoromethyl)pyrryl, ethyl-(1-methylamino-2-nitrovinyl) amido, 2-cyanoimino-1,3-thiazole alkyl. The invention also discloses structures of the compounds and effects of preventing and treating agricultural diseases, as well as application of the compounds serving as insecticides.
Description
(1) technical field
The invention belongs to pesticide field, technical scheme relates to one group of thiophosphoryl compound, is specifically related to one group of thiophosphoryl compound and preparation method thereof and take its sterilant application that is activeconstituents.
(2) background technology
Aryl-pyrrolidine carbonitrile derivatives, phosphorothioate derivative are effective sterilant, miticide and invertebrate poison.Due to the higher problem of toxicity, the use of Determination of Organophosphorus Pesticide is restricted, so new strategy and thinking are expected in the research and development of organophosphorus pesticide.According to pesticide molecule principle of design, we,, by organic phosphorus active group and the splicing of other biocidal activity groups, have designed and synthesized one group of thiophosphoryl compound.Biometric data shows that invented new compound has certain insecticidal activity.The waste water producing in new compound building-up process is less, and is easy to process, and while producing as sterilant, relatively environmental protection, is beneficial to industrialization and Serve " Agriculture.
(3) summary of the invention
The object of this invention is to provide one group of thiophosphoryl compound, structure is as shown in I formula:
Wherein, X is S or O; R
1for ethyl or the chloro-4-bromophenyl of 2-; R is any one in sub-methoxyl group-2-(rubigan)-3-cyano group-5-(trifluoromethyl) pyrryl of S-3-methyl-2-(4-chloro-phenyl-) butyryl radicals, 4-, 4-methylene sulfenyl-2-(rubigan)-3-cyano group-5-(trifluoromethyl) pyrryl, ethyl-(1-methylamino-2-nitroethylene base) amido, 2-cyanoimino-1,3-thiazoles alkyl.
Concrete, thiophosphoryl compound provided by the invention (I formula) structural formula is as shown in table 1.
Table 1 thiophosphoryl compound provided by the invention concrete structure
Another object of the present invention is to provide described thiophosphoryl compound synthetic method, and concrete preparation method is shown in the embodiment of the present invention 1～embodiment 5.
It is agricultural insecticide application that a further object of the present invention is to provide described thiophosphoryl compound.
The invention has the beneficial effects as follows: described thiophosphoryl compound provided by the present invention can be obtained certain prevention effect for preventing and treating Agricultural pests.
It is one of key characters of the present invention that described thiophosphoryl compound of the present invention is used for preventing and treating Agricultural pests.
(4) embodiment
The present invention is by preparation and the biological activity of specific preparation and biological activity determination embodiment specific description five kinds of thiophosphoryl compounds of the present invention, and described embodiment is unrestricted the present invention for specific description the present invention only.
The experimental technique using in following embodiment if no special instructions, is ordinary method.
In following embodiment, material used, reagent etc., if no special instructions, all can obtain from commercial channels.
Preparation and the Structural Identification of embodiment 1L100323 (O, O-diethyl-S-[3-methyl-2-(4-chloro-phenyl-) butyryl radicals] phosphorodithioate)
Reaction equation:
Concrete operations: add methylene dichloride 25mL, O in 50mL there-necked flask, O-diethyldithiophosphoric acid 3.7g (0.02mol), ice-water bath is cooling, drip 3-methyl-2-(4-chloro-phenyl-) butyryl chloride 4.9g (0.02mol) and pyridine 1.58g (0.02mol) simultaneously, dropwise continuation low-temp reaction.Reaction finishes, and filters pyridine hydrochloride, washing, dry, precipitation, obtains yellow liquid target product O, O-diethyl-S-[3-methyl-2-(4-chloro-phenyl-) butyryl radicals] and phosphorodithioate, yield 78.2%.
Structural Identification:
1hNMR (500MHz, CDCl
3) δ: 7.29～7.32 (d, 2H, ph-H), 7.20～7.21 (d, 2H, ph-H), 4.10～4.25 (m, 2H, OCH
2), 3.97～4.28 (m, 2H, OCH
2), 3.33～3.34 (d, 1H, CHCO), 2.40 (m, 1H, CHMe
2), 1.19～1.21 (d, 3H, CH
3), 0.67～0.72 (d, 3H, CH
3); IR (KBr): max=2963 (CH
3), 1800 (C=O).
Preparation and the Structural Identification of embodiment 2L100906 (O, O-diethyl-S-[4-methylene radical-2-(rubigan)-3-itrile group-5-(trifluoromethyl) pyrroles] phosphorodithioate)
Reaction equation:
Concrete operations: under ice-water bath condition, add 5ml water, O in 50ml single port bottle, O-diethyldithiophosphoric acid 2.7g (0.014mol) under stirring, adds NaHCO in batches
30.84g (0.01mol), continues stirring reaction 1h, and standing filtration, separates water, obtains O, O-diethyldithiophosphoric acid sodium salt; Get 3.2g (0.01mol) 4-chloromethyl-2-(4-chloro-phenyl-)-5-trifluoromethyl pyrpole-3-nitrile, add in 100ml there-necked flask, toward wherein adding 50ml ethanol, 5 poly(oxyethylene glycol) 400, be warming up to backflow again, slowly add above-mentioned O, O-diethyldithiophosphoric acid sodium salt, 1h dropwises, and continues reaction 3h, stopped reaction, steam solvent, wash to obtain white-yellowish solid; This solid is crossed silicagel column purification (V
hexanaphthene: V
ethyl acetate=5: 1) obtain white solid target product O, O-diethyl-S-[4-methylene radical-2-(rubigan)-3-itrile group-5-(trifluoromethyl) pyrroles] phosphorodithioate.Fusing point 107.0-108.0 ℃, yield 77.5%.
Structural Identification:
1hNMR (500MHz, CDCl
3) δ: 9.29～9.47 (s, 1H, NH), 7.64～7.65 (d, 2H, ph-H), 7.45～7.47 (d, 2H, ph-H), 4.20～4.26 (m, 2H, OCH
2), 4.17～4.20 (m, 2H, OCH
2), 4.11～4.17 (d, 2H, SCH
2), 1.30～1.40 (t, 6H, CH
3); IR (KBr): max=2963 (CH
3), 2224 (CN).
Preparation and the Structural Identification of embodiment 3L090813 (O, O-diethyl-N-(2-cyanoimino-1,3-thiazoles alkyl) thio-phosphamide)
Reaction equation:
Concrete operations: drop into 2-cyanoimino-1,3-thiazoles alkane 3.4g (0.0265mol) in 250mL there-necked flask, add the acetonitrile that 150mL processed to stir, drop into K after basic dissolving
2cO
3solid 3.7g (0.0265mol), slowly drips the 50mL acetonitrile solution of diethoxy thiophosphoryl chloride (94%) 5.3g (0.0265mol), in 15min, dropwises, and is warming up to 45 ℃ of reaction 13h.React complete filtration, filtrate is concentrated, obtains yellow oil and crosses silicagel column (V sherwood oil: V ethyl acetate=7: 3).Re-crystallizing in ethyl acetate obtains colourless transparent crystal L090813.Fusing point 49.2-51.5 ℃, yield 76.9%.
Structural Identification:
1hNMR (500MHz, CDCl
3) δ: 4.22～4.28 (t, 4H, CH
2), 3.41～3.43 (m, 4H, OCH
2), 1.33～1.41 (t, 6H, CH
3); IR (KBr)/cm-1:max=2979 (CH
3), 2241 (CN).
Preparation and the Structural Identification of embodiment 4R090818 (O-ethyl-O-(the chloro-4-bromophenyl of 2-)-S-[4-methylene radical-2-(rubigan)-3-itrile group-5-(trifluoromethyl) pyrroles] thiophosphatephosphorothioate)
Reaction equation:
Concrete operations: in 100ml there-necked flask, pack 26g (0.13mol) into bromine ortho chloro phenol, 50ml chlorobenzene, 12g triethylamine, in 10～15 ℃ of slow 19.5g diethoxy thiophosphoryl chlorides that drip, room temperature reaction 12h, reactant is respectively washed once with 30g3% aqueous sodium carbonate and 30ml water, anhydrous sodium sulfate drying, precipitation.In above-mentioned product, add 52g33% dimethylamine, backflow 5h, steams dimethylamine and obtains brown yellow transparent liquid, this liquid is put to refrigerator and cooled and freeze, and becomes oyster white (jaundice) solid, 97.4g, R90806II after several days.Get above-mentioned white solid 6.35g (0.0157mol) and add 5g (0.0157mol) 2-(4-chloro-phenyl-)-4-chloromethyl--the 80ml acetonitrile solution of 5-trifluoromethyl pyrpole-3-nitrile, 63 ℃ of reaction 5h, cool to room temperature, 90ml is washed to neutrality, obtain the faint yellow dope of 8.5g, acetonitrile recrystallization makes white powder R090818.Fusing point 160.2-160.3 ℃, yield 69.7%.
Structural Identification: 1H NMR (500MHz, CDCl
3) δ 9.48 (1H, s, N-H), 7.62～7.63 (2H, d, 2=CH), 7.54 (1H, s ,=CH), 7.46～7.48 (2H, d, 2=CH), 7.35～7.40 (1H, d,=CH), 7.33～7.35 (1H, d ,=CH), 4.38～4.41 (2H, t, CH
2cH
3), 4.19～4.30 (2H, m, CH
2-S), 1.46-1.43 (3H, t, CH
3); IR (KBr) v:3440,2224,1623,1241,1158,714cm
-1.
Preparation and the Structural Identification of embodiment 5R100902 (O, O-diethyl-N-ethyl-N-(1-methylamino-2-nitroethylene base) is for phosphamide)
Reaction equation:
Concrete operations: in 250ml there-necked flask, drop into 4.05g (0.021mol) diethoxy thiophosphoryl ethamine, 10.87g (containing methylamine 0.105mol) 30% aqueous methylamine solution, 8.70g (0.063mol) salt of wormwood, 80ml toluene, at 17 ℃, drip 3.84g1,1, the chloro-2-nitroethane of 1-tri-, temperature rises, and reaction solution color is by the colourless yellow-green colour that shoals to light yellow, and about 1.1h finishes.Continue insulation reaction 3.8h, stopped reaction.Washing separatory, gets toluene layer concentrated, obtains 6.35g yellow liquid R100902, yield 78.9%.
Structural Identification:
1h NMR (500MHz, CDCl
3) δ 7.18 (1H, s ,=CH), 4.01～4.11 (4H, m, (OCH
2cH
3)
2), 3.01 (1H, s, NH), 2.98～3.00 (2H, q, NCH
2), 2.35 (3H, s, NHCH3), 1.31～1.34 (6H, t, (OCH
2cH
3)
2), 1.12～1.14 (3H, t, NCH
2cH
3); IR (KBr) v:3357,2979,2934,2905,1391,1121,1030,955,781cm
-1.
The virulence effect of the prepared compound of embodiment 6 example 1～5 to beet armyworm
Toxicity Determination adopts leaf dipping method to carry out.Reagent agent is diluted to setting concentration.The blade of removing surface wax layer is cleaned, dried with the bore punch tool identical with 12 orifice plate internal diameters, broken into disk afterwards, flood 10 seconds in liquid, after taking-up, again dry, put into 12 orifice plates, 2, every hole, accesses 3 instar larvaes of neat and consistent.Not contain the space management of medicament (containing solvent and emulsifying agent), compare.Every processing repeats 4 times, and totally 48 examination worms are placed in the incubator of temperature (27 ± 0.5) ℃, humidity (70 ± 10) %, illumination 16L:8D.Within every 12 hours, 24 hours, 48 hours, 72 hours, check dead borer population, the tweezers of take touch the motionless person of polypide larva as dead.
After the medicine of this test, 48 hours blank group mortality ratio are less than 10%, meet the raw requirement of surveying, and are efficiency test.
Five kinds of thiophosphoryl compounds of test compound the results are shown in Table 2 to the toxicity test of 24 hours (1d), 48 hours (2d) of beet armyworm 3 instar larvae, 72 hours (3d).
Wherein, establish bromothalonil for contrast.
The virulence of the prepared compound of table 2 embodiment 1～5 to beet armyworm 3 instar larvaes
The virulence effect of the prepared compound of embodiment 7 example 1～5 to small cabbage moth
With reference to NY/T1154.6-2006, adopt dip method to process, examination worm is inserted and soaked in worm cage, in different liquid medicines, flooded for 8 seconds, then with filter paper, suck the upper unnecessary liquid of polypide, again examination worm is transferred in the plastics insect box that is placed with fresh cabbage leaves, in temperature, be 28.0 ± 1.0 ℃, relative humidity remains on 80 ± 5%, in the illumination box that the photoperiod (L/D) is 16h/8h, raises.Every 24 hours, check the dead quantity of larva, the tweezers of take touch the motionless person of polypide larva as dead.
After the medicine of this test, 48h blank group mortality ratio is less than 10%, meets the raw requirement of surveying, and is efficiency test.
Five kinds of thiophosphoryl compounds of test compound the results are shown in Table 3 to the toxicity test of 24 hours (1d), 48 hours (2d) of small cabbage moth 3 instar larvae, 72 hours (3d).
Wherein, establish bromothalonil for contrast.
The virulence of the prepared compound of table 3 example 1～5 to small cabbage moth 3 instar larvaes
The virulence effect of the prepared compound in embodiment 8:1～5 to apple yellow aphid
With deionized water, the mother liquor preparing is in advance diluted by setting concentration, with little watering can spraying, establish solvent control, parent solution solvents+emulsifier tween 80, solvent (2%)+tween 80 (0.1%).Before spraying, use and remove young aphid, parasitic aphid and alatae.During spraying, want evenly, prevent that aphid from being swept away by liquid or be drowned.Sprayed after a kind of compound, with liquid detergent, carefully scrubbed little watering can, and rinsed twice with clear water, prevented cross interference impact.Process after 24 hours, 72 hours and check respectively and calculate mortality ratio, corrected mortality by survival aphid number.
Five kinds of thiophosphoryl compounds of test compound the results are shown in Table 4 to the toxicity test of 24 hours (1d) of apple yellow aphid, 72 hours (3d).
Wherein, establish bromothalonil for contrast.
The toxicity test result of the prepared compound in table 4:1～5 to apple yellow aphid
The virulence effect of the prepared compound in embodiment 9:1～5 to Bemisia tabaci
Test period is selected in before 8 of mornings or after at 5 in afternoon, now Bemisia tabaci torpescence, is beneficial to and checks aleyrodid number.First check adult whitefly number on wild cabbage, after inspection, with gauze, cover, surrounding fixes with clip.During spraying, open gauze one osculum, with little watering can, at gauze internal spraying, sprayed rear timely sealing, prevent that Bemisia tabaci from flying out.With deionized water, the mother liquor preparing is in advance diluted by setting concentration, be placed in respectively little watering can and spray, establish solvent control, parent solution solvents+emulsifier tween 80, solvent (2%)+tween 80 (0.1%).Sprayed after a kind of compound, with liquid detergent, carefully scrubbed little watering can, and rinsed twice with clear water, prevented cross interference impact.Within after spray medicine 24 hours, 72 hours, 120 hours, check survival aleyrodid number, calculation correction mortality ratio.
Five kinds of thiophosphoryl compounds of test compound the results are shown in Table 5 to the toxicity test of 24 hours (1d), 72 hours (3d) of Bemisia tabaci, 120 hours (5d).
Wherein, establish bromothalonil for contrast.
The toxicity test result of the prepared compound in table 5:1～5 to Bemisia tabaci
Claims (10)
1. one group of thiophosphoryl compound, structural formula is suc as formula shown in I:
Wherein, X is S or O; R
1for ethyl or the chloro-4-bromophenyl of 2-; R is any one in sub-methoxyl group-2-(rubigan)-3-cyano group-5-(trifluoromethyl) pyrryl of S-3-methyl-2-(4-chloro-phenyl-) butyryl radicals, 4-, 4-methylene sulfenyl-2-(rubigan)-3-cyano group-5-(trifluoromethyl) pyrryl, ethyl-(1-methylamino-2-nitroethylene base) amido, 2-cyanoimino-1,3-thiazoles alkyl.
2. thiophosphoryl compound according to claim 1, is characterized in that: have formula I structure, wherein said compound is selected from any one in following table.
3. according to thiophosphoryl compound described in claim 1 or 2, it is characterized in that the concrete synthetic method of compound L 100323 is as follows: under ice-water bath is cooling, to O, in O-diethyldithiophosphoric acid and dichloromethane mixture, drip 3-methyl-2-(4-chloro-phenyl-) butyryl chloride and pyridine simultaneously, dropwise continuation low-temp reaction; Reaction finishes, and filters pyridine hydrochloride, dichloromethane extraction, and washing, dry, precipitation, obtains yellow liquid target product L100323; O wherein, the molar mass ratio of O-diethyldithiophosphoric acid, 3-methyl-2-(4-chloro-phenyl-) butyryl chloride and pyridine is 1: 1: 1.
4. according to thiophosphoryl compound described in claim 1 or 2, it is characterized in that the concrete synthetic method of compound L 100906 is as follows: under ice-water bath condition, in ethanol and 4-chloromethyl-2-(4-chloro-phenyl-)-5-trifluoromethyl pyrpole-3-mixture of nitriles, slowly drip O, O-diethyldithiophosphoric acid sodium salt, be warming up to afterwards backflow, and continue reaction 3h, stopped reaction, steam solvent, wash to obtain white-yellowish solid; This solid is crossed silicagel column purification (V
hexanaphthene: V
ethyl acetate=5: 1) obtain white solid target product L100906; Wherein, 4-chloromethyl-2-(4-chloro-phenyl-)-5-trifluoromethyl pyrpole-3-nitrile and O, the molar mass ratio of O-diethyldithiophosphoric acid sodium salt is 1: 1.
5. according to thiophosphoryl compound described in claim 1 or 2, it is characterized in that the concrete synthetic method of compound L 090813 is as follows: 2-cyanoimino-1,3-thiazoles alkane is dissolved in acetonitrile, adds K
2cO
3solid, then slowly drips the acetonitrile solution of diethoxy thiophosphoryl chloride, dropwises, and is warming up to 45 ℃ of reaction 13h; React complete filtration, filtrate is concentrated, obtains yellow oil and crosses silicagel column (V sherwood oil: V ethyl acetate=7: 3).Re-crystallizing in ethyl acetate obtains colourless transparent crystal L090813; Wherein 2-cyanoimino-1,3-thiazoles alkane, K
2cO
3with the molar mass ratio of diethoxy thiophosphoryl chloride be 1: 1: 1.
6. according to thiophosphoryl compound described in claim 1 or 2, it is characterized in that the concrete synthetic method of compound R 090818 is as follows: in 100ml there-necked flask, pack 26g (0.13mol) into bromine ortho chloro phenol, 50ml chlorobenzene, 12g triethylamine, slowly drips 19.5g diethoxy thiophosphoryl chloride in 10～15 ℃, room temperature reaction 12h, reactant is respectively washed once with 30g3% aqueous sodium carbonate and 30ml water, anhydrous sodium sulfate drying, precipitation; In above-mentioned product, add 52g33% dimethylamine, backflow 5h, steams dimethylamine and obtains brown yellow transparent liquid, this liquid is put to refrigerator and cooled and freeze, and becomes oyster white (jaundice) solid 97.4g after several days; Get above-mentioned white solid 6.35g (0.0157mol) and add 5g (0.0157mol) 2-(4-chloro-phenyl-)-4-chloromethyl--the 80ml acetonitrile solution of 5-trifluoromethyl pyrpole-3-nitrile, 63 ℃ of reaction 5h, cool to room temperature, 90ml is washed to neutrality, obtain the faint yellow dope of 8.5g, acetonitrile recrystallization makes white powder R090818.
7. according to thiophosphoryl compound described in claim 1 or 2; it is characterized in that the concrete synthetic method of compound R 100902 is as follows: in 250ml there-necked flask; drop into 4.05g (0.021mol) diethoxy thiophosphoryl ethamine, 10.87g (containing methylamine 0.105mol) 30% aqueous methylamine solution, 8.70g (0.063mol) salt of wormwood, 80ml toluene; at 17 ℃, drip 3.84g1; 1; the chloro-2-nitroethane of 1-tri-; temperature rises; reaction solution color is by the colourless yellow-green colour that shoals to light yellow, and about 1.1h finishes.Continue insulation reaction 3.8h, stopped reaction.Washing separatory, gets toluene layer concentrated, obtains 6.35g yellow liquid R100902.
8. according to thiophosphoryl compound described in claim 1 or 2, it is characterized in that: the purposes of described compound in sterilant.
9. an agricultural composition, acceptable carrier and/or vehicle in the compound described in its claim 1 or 2 that comprises 0.1～99.9 % by weight and Pesticide Science.
10. the purposes of agricultural composition according to claim 9, is characterized in that: as the purposes in agricultural insecticide.
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| CN105131033A (en) * | 2015-08-10 | 2015-12-09 | 河北工业大学 | N-(1, 2-diphenyl-2-amino)-thiophosphoramide salt and application thereof |
| CN106167502A (en) * | 2016-07-13 | 2016-11-30 | 广西师范学院 | Azetepa compound and preparation method thereof and the application as insecticide thereof |
| CN113788856A (en) * | 2021-10-20 | 2021-12-14 | 青岛农业大学 | Oxime ester thiophosphoryl amine compound and preparation method and application thereof |
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Cited By (5)
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| CN105131033A (en) * | 2015-08-10 | 2015-12-09 | 河北工业大学 | N-(1, 2-diphenyl-2-amino)-thiophosphoramide salt and application thereof |
| CN105131033B (en) * | 2015-08-10 | 2017-05-31 | 河北工业大学 | N (amino of 1,2 diphenyl 2) thiophosphoryl amine salt and its application |
| CN106167502A (en) * | 2016-07-13 | 2016-11-30 | 广西师范学院 | Azetepa compound and preparation method thereof and the application as insecticide thereof |
| CN113788856A (en) * | 2021-10-20 | 2021-12-14 | 青岛农业大学 | Oxime ester thiophosphoryl amine compound and preparation method and application thereof |
| CN113788856B (en) * | 2021-10-20 | 2023-02-21 | 青岛农业大学 | Oxime ester thiophosphoryl amine compound and preparation method and application thereof |
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| CN103554176B (en) | 2016-04-27 |
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